Gelatino silver halide emulsion containing a halogenated aldehyde acid and a perhydrotriazine compound as hardening agents

ABSTRACT

A photographic silver halide emulsion element comprising a gelatin layer including therein as a combination of hardening agents, a hexahydro-1,3,5-triazine carrying at least two Nvinylcarbonyl or N-vinylsulphonyl groups, mucochloric or mucubromic acid is described. The hardening of the gelatin layer is rapid without loss of permeability to processing solutions and with no after-hardening occurring.

United States Patent [19 Velter et al. l 1March 20 1973 GELATINO SILVER HALIDE [56] References Cited EMULSION CONTAINING A HALOGENATED ALDEHYDE ACID UNITED STATES PATENTS AND A PERHYDROTRIAZINE 2,994,611 8/1961 Hegna et al. ..96/1 11 COMPOUND AS HARDENING AGENTS 2,080,019 5/1937 Wh1te 3,255,000 6/1966 Gates et a] ..96/l l 1 [75] lnventors: Raphael Joris Velter, Mortsel, Belgium; Karl-Otto Meyer, Leverkusen, FOREIGN PATENTS OR APPLICATIONS Germany 860,323 2/1961 Great Britain ..96/1 11 [73] Assignee: Gevaert-Agfa N.V., Mortsel, Belgium Primary Examiner.l. Travis Brown Assistant Examiner-Won H. Louie, Jr. [22] 1970 Attorney-Brufsky, Staas, Breiner and Halsey [21] Appl. No.: 11,789

[57] ABSTRACT Foreign Application Priority Data A photographic silver halide emulsion element com- Feb. 24, 1969 Great Britain ..9,s1 1/69 prising gelatin layer including therein as a comma;

tion of hardening agents, a hexahydro-l,3,5-triazine 52 us. c1. ..96/lll, 260/117, 106/125 carrying a! least two N-vinylcarbonyl or y 511 Im. 01. ..G03c 1/30 sulphonyl groups. mucochloric or mucubromic acid is 581 Field 61 Search ..96/1 11; 260/117; 106/125 described The hardening of e gelatin layer is rapid without loss of permeability to processing solutions and with no after-hardening occurring.

7 Claims, No Drawings GELATINO SILVER HALIDE EMULSION CONTAINING A HALOGENATED ALDEHYDE ACID AND A PERHYDRO'IRIAZINE COMPOUND AS I-IARDENING AGENTS The present invention relates to an improved method of hardening photographic gelatin layers and silverhalide emulsion layers containing gelatin as binder. I

In the preparation of photographic gelatin dispersions and gelatino silver halide emulsions it has been the practice to treat the dispersions and emulsions, prior to coating, with hardening agents for the gelatin.

Among the compounds that have been proposed for hardening gelatin as such or gelatino silver halide emulsions may be mentioned aldehydes such as formaldehydes, dialdehydes, diketones such as divinylketone, halogen substituted aldehyde acids such as mucochloric and mucobromic acid, hexahydro-s-triazines carrying vinylcarbonyl, halogenoacetyl and/or acyl groups such as l,3,S-triacryloylhexahydro-l,3,5triazine, 1,3- diacryloyl-S -acetyl-hexahydrol ,3 ,S-triazine, 1,3 ,5 trichloroacetyl-hexahydro-l,3,5-triazine, compounds carrying one or more vinylsulphonyl groups such as divinyl sulphone, 1,3,5-trivinylsulphonyl benzene, etc.

Though the mentioned compounds are satisfactory as hardening agents for gelatin, their application for photographic purposes often poses a number of difficulties. Some of them are photographically active while others have a deleterious effect on the physical properties such as the brittleness of the gelatin layers. Moreover some hardening agents have the disadvantageous effect of after-hardening which means that hardening continues for a certain time after the gelatin composition has been coated. It is important that hardening of photographic layers reaches its maximum shortly after drying so that the permeability for processing solutions is not continuously altered as is for instance the case with formaldehyde. Formaldehyde as well as mucochloric acid show a poor compatibility with photographic color emulsions in that the excess of hardener that has not or not yet reacted with the gelatin shows a strong interaction with the color developer and/or the color forming couplers, particular with the 2-pyrazolin-5-one magenta-forming couplers and the benzoylacetanilide yellow-forming color couplers resulting in a reduction of the color density and the formation of undesirable color fog. Furthermore, the organic compounds carrying one or more vinylcarbonyl or vinylsulphonyl groups, the hardening action of which has been ascribed to the vinyl groups often give rise to the formation of fog, a loss in sensitivity and flattening of gradation probably owing to their reducing effect on the silver halide and to their rather slow hardening action the maximum hardening being reached only months after coating, so that the sensitometric characteristics of photographic silver halide materials comprising said compounds as hardening agents, vary upon storing which is most undesirable.

It has now'been found that hardening of photographic gelatin layers can be effected without giving rise to the above deleterious effects by the use of halogen substituted aldehyde acids such as mucochloric acid and mucobromic acid in conjunction with hydrogenated diazines and triazines such as piperazine, hexahydropyrimidine, hexahydropyridazine and hexahydro-l,3,5-triazine carrying at least two N-vinylsulphonyl or N-vinylcarbonyl substitutents including such hydrogenated diazines and triazines carryingv further substituents.

Examples of perhydrodiazine and perhydrotriazine derivatives suitable for use in accordance with the invention with halogenated aldehyde acids as well as methods for the preparation of said derivatives can be found in German Pat. Nos. 872,153 and 1,090,427. Among these compounds l,3,5-triacryloyl-hexahydrotriazine and 1,3 ,5-trivinyl-sulphonyl-hexahydrotriazine are preferred.

The hardening agents applied in accordance with the invention are used in a ratio of halogenated aldehyde acid to perhydro diazine or triazine derivative comprised between 5:l-0.5:l, preferably between 3:1-1 :1.

The total amount of hardening agents used in the photographic gelatin layers may vary within wide limits dependent upon the degree of hardness desired. The said amount of hardening agents is generally comprised between about 0.5 and about 3 percent based on the dry weight of the gelatin.

In the practice of the invention, the compounds are incorporated into the photographic gelatin layers e.g. a gelatino silver halide emulsion layer from a solution in a suitable solvent such as methanol, ethanol, ethylene glycol monomethyl ether, etc. which does not adversely effect the sensitive photographic emulsion; the hardeners are incorporated into the gelatin layers preferably prior to coating. By photographic gelatin layers there is not only meant photographic gelatino silver halide emulsion layers but all kinds of gelatin layers that are used in the composition of a photographic material such as backing or anti-halation layers, protective coatings, filter layers, etc.

The combination of hardeners of use according to the present invention has no detrimental effect on the sensitometric characteristics of the photographic lightsensitive material. Moreover, there is no interaction between the hardening agents and other addenda such as color couplers, sensitizers, stabilizers, etc.

Therefore, the combination of hardeners according to the present invention is of particular value for the hardening of photographic multilayer color materials wherein the color forming couplers are present in a diffusion fast form in the emulsion layers of said material or in gelatin layers in water-permeable relationship with said emulsion layers.

Moreover hardening reaches its maximum more rapidly than when the perhydro triazine and diazine derivatives are used alone and the stability against moisture of the gelatin layers hardened in accordance with the invention is improved as compared with gelatin layers hardened solely with halogen substituted aldehyde acids. 1

The following examples illustrate the present inven-' tion.

EXAMPLE 1 A silver bromoiodide gelatin emulsion comprising g of gelatin per kg is adjusted to pH 6.2 and then di- 1 determined as compared with materials that have been stored under deep-freeze conditions (C). The values of AS are log It values and a value of AS 0.30 means that the sensitivity has decreased with 50 percent.

The following results are obtained.

A7 AD I Hardener 1 Blue Green Red Blue Green Red Blue Green Red 1% of A 0. 10 0. *0. 22 0. 20 0. 06 0. 04 0. 03 +0. 09 +0. 04 0.25% of A+0.50% of B 0.03 0. 09 0.09 0.09 0. 06 0. 03 +0.05

1 A:1,3,5-tziacryloyl-hexahydro1,3,5-triazine (triacrylformal). B=mucoch1oric acid.

come loose from the support is taken as melting point.

The following results are obtained:

Material Melting point After having been stored for 3 days at 22C 36 hours at57C and 34 of reLhumidity 20 1 100C 100C 2 40C 100C 3 100C 100C From these results it appears that with a mixture of 25 hardeners according to the present invention the material is more rapidly hardened than with 1,3,5- triacryloylhexahydro-l ,3 ,S-triazine alone.

It was also found that the material hardened according to the present invention showed better resistance to moisture than the material hardened with mucochloric acid alone.

EXAMPLE 2 days at 22C, is 100C.

After exposure and processing, the material is free from fog and shows, as compared with unhardened material, practically no loss in gradation and speed. The hardened material further shows an excellent stability on storing in that the photographic properties remain unchanged.

EXAMPLE 3 A series of identical photographic multilayer color materials are prepared which materials comprise a support, a red-sensitized silver halide emulsion layer containing a cyan color former, a green-sensitized emulsion layer containing a magenta color former, a yellow filter layer and a blue-sensitive silver halide emulsion layer containing a yellow color former.

The emulsion layers and yellow filter layers of these 7 materials are hardened by means of the hardeners listed in the table below (the amounts are given in percentages by weight relative to the amount of dry gelatin).

The materials are subjected to an accelerated storing test by keeping them for 4 weeks at 35C and 80 percent of relative humidity. The variations in sensitivity (AS), gradation (A7), and maximum density (AD) are EXAMPLE 4 Photographic multilayer color materials as described in Example 3 are stored for 6 months at 20C whereupon the variations in sensitivity (A S) and gradation (A7) are determined as compared with materials that have been stored under deep-freeze conditions (15 C).

The following results are attained.

Hardener A S A 7 blue green red blue green red 1%ofA 0.l0 0.17 0.l7 -O.-l2 0.090.l0 0.25 of A 0.04 0.09 -0.07 0.03 0.0-H).01 0.50 of B From the foregoing examples 3 and 4 it is clearly apparent that the multicolor material hardened with the combination of hardening agents according to the present invention shows improved storage stability over the multicolor material hardened with triacrylformal alone.

What we claim is:

1. A photographic silver halide emulsion element comprising a gelatin layer including therein as hardening agents a hexahydro-l,3,5-triazine carrying at least two N-vinylcarbonyl or N-vinylsulphonyl groups and a member selected from the group consisting of mucochloric acid and mucobromic acid, the ratio of the said mucobromic or mucochloric acid to said hexahydro-l ,3,5-triazine being from about 5:l0.5:l.

2. The photographic element according to claim 1 wherein the gelatin layer includes the silver halide emulsion.

3. The photographic element according to claim 1 wherein the gelatin layer is in water-permeable relation to the silver halide emulsion.

4. The photographic element according to claim 1 wherein the said hardening agents are present in said layer in a total amount of from about 0.5 and 3 percent by weight of dry gelatin in the said layer.

5. The photographic element according to claim 1 including a color forming coupler compound in the silver halide emulsion.

6. The photographic element accordingto claim 1 wherein said hexahydro-1,3,5-triazine is a member selected from the group consisting of 1,3,5-trivinylsulphonyl-hexahydro-l ,3 ,S-triazin'e and 1,3 ,5- triacryloyl-hexahydro-l ,3 ,S-triazine.

7. The photographic element according to claim 1 wherein the ratio ofsaid mucobromic or mucochloric acid to said hexahydro-l,3,5-triazine is from about 3:l l:l.

i t i l 

2. The photographic element according to claim 1 wherein the gelatin layer includes the silver halide emulsion.
 3. The photographic element according to claim 1 wherein the gelatin layer is in water-permeable relation to the silver halide emulsion.
 4. The photographic element according to claim 1 wherein the said hardening agents are present in said layer in a total amount of from about 0.5 and 3 percent by weight of dry gelatin in the said layer.
 5. The photographic element according to claim 1 including a color forming coupler compound in the silver halide emulsion.
 6. The photographic element according to claim 1 wherein said hexahydro-1,3,5-triazine is a member selected from the group consisting of 1,3,5-trivinylsulphonyl-hexahydro-1,3,5-triazine and 1,3,5-triacryloyl-hexahydro-1,3,5-triazine.
 7. The photographic element according to claim 1 wherein the ratio of said mucobromic or mucochloric acid to said hexahydro-1, 3,5-triazine is from about 3:1- 1:1. 